Formal Intramolecular (4+1)-Cycloaddition of Dialkoxycarbenes: Control of the Stereoselectivity and a Mechanistic Portrait

被引：26

作者：

Beaumier, Francis ^{[1
]}

Dupuis, Marianne ^{[1
]}

Spino, Claude ^{[1
]}

Legault, Claude Y. ^{[1
]}

机构：

[1] Univ Sherbrooke, Dept Chim, Sherbrooke, PQ J1K 2R1, Canada

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 13期

基金：

加拿大自然科学与工程研究理事会;

关键词：

FISCHER CARBENE COMPLEXES; VINYLCYCLOPROPANE-CYCLOPENTENE REARRANGEMENT; METAL-PROMOTED VINYLCYCLOPROPANE; ACCEPTOR-SUBSTITUTED VINYLCYCLOPROPANES; ELECTRON-DEFICIENT 1,3-DIENES; 4+1 CYCLOADDITION REACTIONS; PSEUDO-LARIC ACID; TU-JIN-PI; VINYL ISOCYANATES; NUCLEOPHILIC CARBENES;

D O I：

10.1021/ja211927b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The stereoselective synthesis of 5-5, 6-5, and 7-5 fused O-heterocyclic compounds is reported. The key reaction is a formal intramolecular (4 + 1)-cycloaddition involving a dialkox-ycarbene and an electron-deficient diene where the stereo-selectivity is dependent on the length of the tether. An analysis of the stereochemical outcome of this reaction sheds light on its complex mechanistic picture. High-level calculations were used to support the proposed mechanistic portrait.

引用

页码：5938 / 5953

页数：16

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